CA2077828A1 - Silicone polyether alkyl copolymer synthesis - Google Patents

Abstract

ABSTRACT OF THE INVENTION

There is disclosed novel silicons polyether alkyl copolymers, and a method for their preparation, for use as emulsifiers in improved stability water-in-oil emulsions.

Description

- 2~ 3'~.~
-1- 60SI~ 23/2R

SILICONE PO~YETHER ALKYL COPOLYMER SYNTHESIS

The present invention relates to novel polysiloxane-polyether copol~mers and their use in stabilizing water-in-oil emul~ions, such as poli~he~ and antiper~pirant composition~ of the ~o-called dry-feeling t~pe, comprising an amulsion of watar in a volatile, water-insoluble liquid~

BACKGROUND OF THE INVENTION

A variety of poly~iloxane-polyether or poly~iloxane polyoxyal~ylena copolymers ar~ known in tha art, and the copolymers have found many u9e8 including the manufacture of polyurethane foams and emulslfication of one of a pair of immlscibl~ liquids in the other, such a~
wa~er-in oil, oil-in-water and o~l-ln-oll emul~ions.
~hQ U3Q of polysiloxanQ surface active agents compri~ing organic poly~her groups to stabilize emul3ion~
is well known. Unit~d States Pate:nt ~o. 4,421,656 disclose t~rpolymeric polydiorgano~iloxane~ a~ stabilizer3 for solid -free lnv2rt emul~ion~ for the deep well-drilling ar~. Uni~ed State~ Pa~ent No. 4,254,878 use~ a poly3iloxana ~urface actlve agent to stabilize anSiper~pirant ~tick compo~ltion~. United State~ Paten~
~o. 4,218,250 u3es such a polysiloxan~ ~ur~acs active agen~
to ~tabiliz3 poli h fonmula~lon~. United States Patent ~o.
4,268,499 uses such ~urface activ~ agent3 to ctabilize antiper~pirant emul~ion compo~ition~. Further, United States Patent No. 4,311,695 u~e3 ~uch urfac~ a~tiva agents in per~onal care cream and th~ like.

~ ~ ~J~

Special mention is made of United States Patent No. 5,008,103, which disclose3 poly~iloxane containing organic polyether groups. However, the polysiloxanes of the present invention have improved stability when employed with mineral oils, cyclic methylsiloxane fluid~ and the like in water-in-oil emul~ion~.
Polysiloxane surfa~e active agents are sometimes referred to a~ polysiloxane-polyoxyalkylene copolymer~.
However, their u~e to date as stabllizar~ for silLcone emul~ion~, particularly water-in-oil emul~ion~, ha~ not always been ~ompletely ~ati~factory becau3e the variable~
af~ecting their function ar~ not well understood. Water-in-oil emul~ions whlch contain high concentrations of salt~
or other ionlc material3 are often particularly difficult to ~tabilize. The problems encountered in formulating emulsion~ of antiper~pirant~ in volatile fluid~ ara exemplary of thi~.
Antiper~pirant compoqitions are well known in the cosmetic art. The~e compositions are formulatad a~
aero~ol~, gels, sticks, cr~a~s, pump ~prays and lotion3 and compri3s an a~tringent, typically comprising one or more zirconiu~ saltrs and/or aluminum ~5alt~, in variou~ forms such as dry, impalpable powder, an alcohol ~olution or an aqueou~ solution. O~ the~a variou~ forms of astringents, tha aqueou~ solution i~ ganerally con~idered to bs the most ef f ec~iv~ antiper~pirant.
An antlpar~pir~nt compo~ltion having water as the continuou~ phas~, sush a3 an agueou~ 301ution of an astrln~ent, or an oil-in-water type emul3ion thereof~ i~
les~ de~irable be~ause it tend~ to feel wet when applied to the human skin and to go through a tac~y ~tate during the drying period after application. Therefor~ ~he u~e of water-in-oil emulslons to apply antiperspirant~ to tha sXin ha~ found favor.

2~

United State~ Patent No. 4,122,029 disclo~es water-in-oi~ ~ype composi~ion~ having broad utility and compri~ing a polydiorganosiloxane-polyoxyalkylene copolymer and a water-in-oil type surfactant. When formulated as an antiper~pirant emul~ion of an aqueou3 solution of an astringent such a~ aluminum chlorohydrate emulsified in a volatile, non-aqueou3 contlnuou3 phase, these composition~
have a desirabl~ dry feeling when applied to the human skin.
United sta ~ e3 Patent No. 4,268,499 di~clo~es compositions de~cribed a having greater efficacy than those of United States Patent No. 4,122,029. The e~icacy was d2termined by applying composition~ to sub~ects' wrists and measuring the ~ime requir~d for thQ compo~ition to dr~
and turn white.
Another t~pe of water-in-oll emulsion which has found favor with the public i-~ poli~hes, particularly for furniture. One drawback to furniture polishe~ which utili7e organic or organosilicone surfactants comprising long chain oxyalkylene residue~, particularly long chain oxyethylene re~idue~, is that thl3 surfactant may tend to a~tack tha finish of th~ article to be polished. Thi~ i~
particularly the ca~e when tha flni~h i~ ~a~ed on nitrocellulo3~ lac~uer~, ~inc~ gly~ol ether~ are ~olventQ
of choice for nitrocQllulo e fini~he~.
Ther~ has now b~en found a novel family of sillcon~ polyether/alkyl copol~mers which exhibit signiflcant improvemQnts in forming a wide variety o~
wat~r-in-oil e~ulsion~ for u~e in product3 ~uch as antiper~pirantR, h~ir ~hampoo~ or conditioner~, hand cream~, lotion~, tanning oil~ and poll~hes (au~o and furniture). Surprislngly, water-in-oil emul ion~ employing tho ~ilicone poly~ther copolymer emulsifier~ o~ the pre~ent invention, exhibit Rignificantly improved ~tability over prior art emul.sions when ~mul~fied with mineral oil~O
cyclic m~thyl siloxanes and othsr oily ph~o emolli0nt~, SUM~ARY OF THE INvENrIoN

According to the present invention there is provided a silicone polyether alkyl copolymer water-in-oil emulsifier of the g~neral formula:
MD'xD"yM
wherein: M represents trimethylsiloxy ~ndcapping units; D' representa alXyl siloxy unit~ of the general formula t C~3 ) R'SiO2~2 wher~ R' i9 an alkyl group having from 6 to about 30 carbon atoms; D" i~ an oxyalkylene siloxy unit of the ~eneral formula (H3)R2SiO2,2 where R2 i$ a polyoxyalkylene ether re~idue of th~ formula -~R4)p-(oR3)n-oRs wherein each individual R~ is an alkylene radical having from 2 to 6 carbon atom~, R' is an alkylene radical having from 2 ~o 20 carbon atoms, R5 i~ a hydrogen atom or a hydrocarbon radlcal of from 1 to about 12 carbon atoms, n has a value of from about 5 to about 20, and p ha~ a value of zero or l; and x i~ from 1 to about 29 and y is from l to about 29 wl~h the proviso that: x+y i~ from about 2 to about 30.
Preferably, x i~ from l to about 20, y i~ from 1 to about 20 and x+y i5 from about 15 ~o about 25. Most preferably x i~ 16, y i~ 4 and x+y i3 20.
Al~o according to the present inv3ntion, there is provided a proce~3 ~or prep~ring the silicon 2S polyether/alkyl copolymers of the pre~e~t lnvent~on, the proce~s compri~ing th~ following step~ conducted in sequ~nce-(a~ r~acting a ~ilicon~ hydrid~ fluid of the formula MDqM (I); wherein M reprssent~ trimethylsiloxy endc~pping units, D r~pres2nts mathylhydrosiloxy unit~ and q repre~ents an integer of from abouk 2 to about 30, with a first portion of an alpha ole~in o~ from about 6 to about 30 carbon a~om~ tc form a compound of th~ formula:

MDq~D'~ (II); wherein M, D and q are a~
above defined; D' repre~ents an alkylsiloxy unit of the formula CH3R'SiO wherein R' represents an alkyl rad~cal of from about 6 to about 30 carbon atom~ and f i3 from about 1 to about 29;
(~) reacting a compound of formula ~II) with an allyl polyether of from 2 to about 12 carbon atoms to form a compound of the ~o~mula: MDq~yD'~"yM (III);
wherein M~ D, D', q and f ara as above defined, and D"
representY an oxyalkylene ciloxy unit of the general formula (CH3)R2SiO2,2 where R2 i-~ a polyoxyalkylene ether r~sidue of tha formula -(R~)p-( oR3 ) n~OR5 wherein each individual R3 is an alkylane radical having from 2 to 6 carbon atom~, R4 i~ an alkylene radical having from 2 to 20 carbon atom~, R~ is hydrogzn or a hydrocarbon radical of from 1 to about 12 carbon atom~, n has a value of from about 5 to about 20, and p has a value of zero or 1, and y i~ from about 1 to about 29; and (c) reac~lng the compound of formula (III) with a second portlon of 3aid alpha ole~fin to form a compound of tha formula: MD'xD"yM (IV); wherein M, D', D"
and y are a3 defined above, and x is from 1 to about 29 and i~ equal to q-y; and wher~in ~aid ~teps (a), (~) and (c) are carried out in the pr~sencs of a small effective amount of a catalyst for effectlng sald reaction D~TAILED D~SCRIPTION OF ~HE PRESENT INVEN~ION

The novel poly~lloxane copolymer~ of th~ present invention are long chaln hydrocarbon-modif$ed polydiorgano~iloxane polyoxyalkylene copolymer~ cont~ining polydimethyl~iloxy group~, on average at l~a~t one long-chain alkyl~methyl)~loxy group, and on average at least one pQlyoxy~lkylsne group, havlng the general formula MD ' xD " yM
wherein:

M repre~ents trimethylsiloxy endcapping units;
D' represents alkyl siloxy units of the general ~ormula ( C~3 ) R'~l02~2 where R' ~ an alkyl group havlng from 6 to about 30 carbon atoms, D" is an oxyalkylen~ ~iloxy unit of ~he general formula (CH3)R2Sl02~2 where R2 i9 a polyoxyalkylen~ ether re~ldue of the formula -(R~) -(oR3)n-oR5 wherein each lndlvldual R3 is an alkylene radical having from 2 to 6 carbon atoms, R~ is an alkylene radical havlng from 2 to 20 carbon atom~, -R5 i~ a hydrogen ~tom or a hy~roc3rbon radical of from l to about 12 carbon atoms, n ha~ a value of from about !5 to about 2~, and p has a valua o~ zaro or 1;
x i~ from 1 to about 29; and y i~ from 1 to about 29;
with tha provl~o that x+y i3 from about 2 to 5 abou~ 30.
repr~sen 5 hydro3iloxy endcapplng units. ~ 13 ~enarally of the formula (CH3)2R6SiO2~ where R6 may be an alkyl group havlng ~rom 1 to 30 carbon atoms.
Preferably the radical R6 of the ~nd-blocking group M is a lower al~yl group, or el~e an alkyl group derived ~rom ~hc ol~ln used to form thQ R' grol~p3 of the D' moiety, or an R2 group derived from tho polyether u~ed to fvrm ~2 group~ when the poly~llox~n~ containlng ~ilicon hydride groups i~ end-blocked with dim~thylhy~rog~n siloxy group It 13 pre~srred however to utilize a polys110xane ~tar~ing material which i~ end-blocke~ wlth trimethyl~iloxy group3, ln which ca~ R6 i~ m~thyl.

2~

D' repre~2nt~ alkyl siloxy units of the gener~l formula (C~R'S1O2~2 whare R' i~ an alkyl group having ~rom 6 to 30 car~on atom~. Preferably, R' i5 an alkyl group of from B to 18 carbon atom~, and mo~t preferably, ~ decyl and D' i~ m~thyld~cyl~iloxy.
The preferred polyoxyalkylens R2 se~ments con~i~t sol~ly of oxyethylen~ units of th~ formula -CH2-C~2O-, i.e. R3 is ethylene. It furthar i~portant h~rein that the number of rQpeatlng unit~ of -OR'-, i.eO, the value of n, be between abou~ 5 and about 20. Thu~, in the ca~e of ethylene oxld~ a~ th~ repeating unit, the molecular weigh~ of R2 should be less than about 900. The prefe~ed value of n i~ ~rom 10 to 15, which likawi~e for ethylene oxide prov~de3 a molecular weight for R~ of no mor~ th~t about 700.
R~ is ~he group which bond~ the polyoxyalkylene ~egment to the poly~lloxane. R' m~y be -CH2CH2CH2-, -CH2CH2-, -CH~CH2CH2CH2-, etc. Preferably, R, i~ -CH2CH2CH2-. Whan "p"
is zero, the segments are ~oined by -O- which i~ the product of a conden~atlon reactl-on between a cond~nsable substitu~nt on th~ poly~ilox ne and a con~ensabl~ end group on the polyalkylene oxlde. Although the composit~on~ of the pre3ent invent~on are not ~oluble in wa~er, and therefore not sub~ected to vigorou~ hydrolysis cond~t~on~
25 ln e~ulsion~ employing the compo~ition of the present invention, it i~ preferred that "p" be 1, avoid~ng th~ u~e of th~ hydrolyz~bl~ c~rbon-oxygen-silicon bond to link the polyoxyalkylena re~idu~ to the polysiloxane chain.
R5 i~ tA~ terminal group o~ th~ polyalkylen~
ether. Th~ typ~ of ~5 i~ not crltic~l and may ~e sele~ted from hyflrogen, m~thyl, e~hyl, propyl, butyl, phenyl, ace~yl, etc. Pre~erably Rs i~ hydrogsn.
A particularly preferred alkyl siloxy unit D" is me~hyl polyethoxy Yilo~y ha~ing an averag~ R2 molecular weight of from about 30~ to about 8Q0.

-8- 60SI-1423~28 The copolymer~ of the pressnt invention h~ve value~ for x and y which are indep~nd~ntly each from 1 ~o about 29 and re requlred to add up, x+y, to from about 2 to about 30. Prefer~bly x and y aro ea~h independently from 1 to about 20 and x~y is from about 15 to about 25.
Most preferably x is 16 and y is 4.
The present invantion i~ also dlr~cted to a novel methad for forming the ilicon poly~ther alkyl copolymer~
o~ ~he present inYentlcn. T~e nov~l method comprlses the followlng stepq conducted in s~quence:
(a) r~ct~ng a silicone hydrlde fluid of the formula MDqM ~ I ) wher~ln:
M repre~ents tr~methylsiloxy endcapping units, D repre3ents m~thylhydro~lloxy un~t~ and q rQpresQnt~ an integer o~ i'rom about 2 to about 30, w~th a first portion of an alpha olefln of from about 6 to about 30 carbon atoms to form a compound of ~he formula:
MDq~Dl~ (II) wh~rein:
M, D and q ara a~ above defined;
r~p~ssRn~s an alkylm~thylsiloxy unit of the formula C~3R'SiO
~5 wh~rQln R' repres~nt~ an alkyl radical of from about 6 to abou~ 30 ~arbon atom3; and f i~ from about 1 to about 29;
(b) r~acting a co~pound of formula (II) with an allyl polye~her o~ from ~ to about 12 carbon atom~ to form a compound of the ~ormula:
MDq~yD'~'`yM (III) wh~rQin:
M, D, D', q and f are a~ abov~ defined, and --9~ OSI-14~3/28 D" repre~ents an oxyalkylene siloxy unit of the general formula (CH3)R2SiO2~2 where R2 is a polyoxyalkylene ether re~idue of the formula - ( oR3 ) n~OR
wherein each lndividual R3 i~ an alkylene radical having from 2 to 6 carbon atoms, R~ is an alkylen~ radical having from 2 to 20 carbon atom~, R5 i3 hydrog~n or ~ hydrocarbon radical of from 1 to about 12 car~on atoms, n ha~ a value of from about 5 to about 20, p ha~ a value of zero or 1, and y i-~ from abou~ 1 to about 29; and (c) reacting the compoulld of formul~ (III) with a second portion of said alpha ole~Ein to form a compound of the formula:
MD' D" M (IV) wharein:
M, D', D" and y are a~ d~fin~!d above, and X i3 from 1 to about 29 and i3 equal to q-y;
and wh~rein ~aid ~t~ps (a), (b) and ~c) are carrled out in the pr~ence o~ a small ~f~ective amount of a catalyqt for eff~cting ~aid reaction~.
Tho m~thod for preparing th~ polydiorgano~iloxans co~pon~nt g~nerally comprise3 reacting a methyl s~loxane having tarmin~l and/or in-~hain ~illcon-bonded hydrogen atom~ wi~h a fir3t por~on o~ an olefin having ~rom 6 to 30 carbon atom~, such a~ l-oc~en2, l-d~cen~, l-oc~adecen~ or -dodecen~, then with an 012finically term~nated poly-oxyalkylen~, such a3 polyoxyethylen~, and then with a second portion of the alpha olefin~ all in the pre~ence of an Q~fective 2mount o~ a platinu~-~on~ining cataly~t, such as a chloroplatlnic ~cld, i.~. H2P~C16 6H20. In this me~hod the first portion of olefin, the olefinically terminated polyoxyalkylene, and the second portion of olefin are reacted sequentially, first portion of olefin first, with the methyl~iloxane con~ain~ng silicon-bonded hydrogen radicals. It is to be under tood that the polydiorganosiloxane~ that have been prepared in this preferred manner can contain small amount~ of unreacted olefin and/or olefin-terminated polyoxyalkylene.
Any catalyst known to those ~killed in the art for effecting the copolymerization reaction3 of the pre~ent invention may employsd herein. The~e catalysts are descr~bed in th~ literature, e.g., Lamoreaux, U.S. Pat. No.
3,220,972. Platinum ba~ed cataly~ts ar~ preferred.
Pre~erably the amount of cataly~t i~ pre~snt in an amount ranging from about 0.05 to 0.5 weight percent based on the weight of tha ~tarting hydrogen silicon hydrida.
In preferred embodiments, the first and second portions o~ the alpha olefin repre~snt ~ub~tan~ially equivalent amounts of tho ~ame alph~ ole~in. Most preferably the alpha olefin is l-decene and the allyl polye~her i3 an allyl initiated all ethylen~ oxide polyether, hydroxy cappad of average 550 molecular welght.
ThQ silicon polyether alkyl copolymer~ of the present inv~ntion can b~ u~ed a3 emul ~fier3 to form the novel water-in oll emul~ions of the pre~ent invention. The novel water-in-oil emul~ions of th~ present invention g~nerally compri~e (~) from about 10 to about 50 part~ by weight of an oily pha~e; (B) from about 40 to about 80 parts by welgh~ of a di~continuous phase and (C) from about 1 to about 15 part3 by we~ght the ~ilicon polyethar alkyl copolymar emulsif~ers of th~ pre~ent invention.

8~3 Component A of the water-in-oil emulsions o~ the pre~ent inventlon can comprise a wide variety of emollients, such as parafinic hydrocarbon liquid~, mineral o11s and petrolatum. ~Aese ar~ well known in the chemical and polymer art~ and are available commercially.
The oily phase may also compri~e~ a volatile liquid having a normal boiling point less than 250C., the volatile liquid being ~elected from methylsiloxane fluids having the average unit formula ~CH3)~SiO~ 2 wherein a ha~
an average valuc of from 2 to 3 inclusive. Preferred siloxane unit~ are ~lected from the group con~isting of (CH3)3SiOv2~ (CH3)2SiO2~2, CH3SiO3~2 and SiO~2 units-Preferably, tha volatile methyl~iloxane fluid consists e~entially of dimethyl~iloxane units, and option~lly, trimethylsiloxane unit~. Of particular valu~ a~ volatile liquid (A) are the cyclic ~iloxane3 of the general formula ((CH)2SiO)b and tho linear siloxanel~ o~ the genoral formula (CH3)SiO((CH3)2SiO)CSi(CH3)3, and th~ir mix~ures, wherein b i~
an integer of from 3 to 6 and c i~ an integer of from 0 to 4. A highly preferred methylsilox,3ne fluid i~ a mixture of said cyclic 3iloxane~ wh~rein a ma~or portion is tetramer (b = 4 or 5).
Component B of the wat~r-in-oil emul~ionc of the pre~ent invsntion i3 th~ di~continuou3 phas~. Mo3t pr~ferably th~ di~continuou~ pha~ comprise~ water.
~ owever, it i~ also contemplated that the diYcontlnuous pha~e compri~e~ llguid m~dla oth~r than water. Sultabl~ oth~r liquid media ~re org~nic compound~
~uch a~ alcohols, including m~thanol, ethanol, phenol, ethyl~ne glycol, propylene glycol, glycerine, their partlal ether~ and par ial e~ter~; nitrogen compounds including amide~ such aY formamide, acetamide, N,N-~imQthyl formamida and urQa; nltrile~ such a~ ace~onitrlle, and amines and thelr ~alts; acids ~uch a~ formi~ acid, acetic acid, b~nzoic ac~d, ~tearlc ac~d and ~thylene diamin~tetxaac~tic 3~

acid; and ethers such as furan, tetrahydrofuran, dioxane, ethylene glycol dimethyl e~her, propylene glycol dimethyl ether and their pol~meric forms such a~ triethylene glycol diethyl ether. ~ixture~ of any of the foregoing and mixtures of any of them with water are contemplated by the present invention.
Emulsion compositions of this invention wherein the aqueou3 pha~e comprlses wat~r and/or ethanol are particularly use~ul. In common w~th oil-in-water emulsion~, w~ter-in-oil emulsions are de~irable from an economic, safety and environmental viewpoint as a means of preparlng, storingO shipping and u~ing efficaciou~
components. In addition, emuls$on composition~ of aqueous or ethanol solutlon~ have value a~ personal car3 compositions.
It i~ further contemplate~d that the aqueouq phase can compri~e small amounts o;E additives, such a electrolyteY, incorporated therai.n. Preferred i9 from about 0.5 ~o about 5 part3 by welght of sodium chloride.
The emulsions of the pr~qent inventlon may also comprise a wide variaty of ef~icaclous addltives tD) for imparting de~ired charac~eristic~ on the emul~ion~
depending upon the end usa. Pr~ferred addltives are selected from the group con~i~ting of an antiperspirant, a humec~ant~ an in~ect repellent, an odorant, a deodoran~, an emolll~nt, an an~iseptic, a sun~creen, a clean3ing agen~, a Rui~able phanmaceutl~al, a p~gment, a biocid~ and mixtures o~ any of the foregoing.
Praferred are sun~creen3 3uch as titanium dioxide and W A and UYB type sunblockQ These and others are well known to thos~ skilled ~n the art and are available commarcially. Pr~erably th~ typ~ and a~ount of 3un~creen addltive~ are suffi~ient to provide a ~un protection factor of greater than 10, most preferably at least about 15.

Z~!~)J~3~

Al~o preferred are antiper~pirant additive~.
Preferably the antiperspirant additive is a water soluble astringent antiperspirant agent. Example~ of well known a~tringent~ include aluminum, hafnium and ~iroonium salt , such as zirconyl hydroxide halide~, aluminum zirconium chloride, zircon~um-aluminum lactate, ba4ic aluminum halide3 such as Al2(0H)sCl, aluminum bromide and the several water, alcohol or glycin~ complexe~ thereof.
The amount of a~tringent that i3 employed may vary widely and ic not critical; howsver, certain practical limitation~ exi~t. on the on~ hand an efficaciou~
antiperspirant composition would contain sufficient a~tr~ngent to provid~ ~weat reductlon, although compositions containing le~s astringent arQ useful a~
personal care compo3itions. Preferably, the anti-p~r~pirant composition compri~e~ approxim~tely 15 - 30 w~ght percent astringQnt. On the other hand, it is desirable to maximize ~he amount: o~ water in the anti-perspirant formulation without negatin~ utility, for obviou~ economic reason~. Depending on tha particular astringent u~ed, the amount of astringent may vary in concentration in the aqueou~ pha~3~ from aq little as one part by waight astring~nt pQr three part~ by weight water up ~o a saturat~d aqu~ous solution of the a~tringent.
The emul~ion~ of tho present invention are suitable for u~e, without further proce~sing, as a lotlon, pre~r~bly pack ged and disper~ed as a roll-on antlperRpirant co~posit~on. ~owever, gel, aerosol and pump spray ~ormula~ion~ m~y be prepared thersfrom u~ing well known ad~uvant~ 3ueh as alcohols for gel formation and ~olvent3 to reduce th~ vi9~0~ity of ~he formulation le~
than 100 centipolse at 25C. for aero~ol and pump qpray use.

2~ ,B

The emulsion~ of the pre~ent invent~on may be prepared by mixing the proper portion~ of the individual component~ in any order. Although the compositionq of the invention are delineated ln terms of an aqueous Rolution (A) emulsi~ied in a volatile liquid (B) using an emulsifier (C), the emulsion~ can be formed by prepar1ng an aqueous phase, and by preparing an olly pha~e comprising ~he volatile liquid (B) and the emulæifier (C~, and thereafter mixing the aqueou~ phas~ and the oily phase. Mixing may be done u~ing ~tandard emulsi~ying me hods. Optionally, the emulsion~ may be further homogenized~ It is also contemplated that a second conventional emul ifier may b~
added.
The addltiva (D) is added aithar to the aqueou~
phase, a3 in the case o~ astringent~, or to th~ oily pha~e, as in the ca3e of ~unqcreens, depending upon the type .o~
addltives a3 known to those ~killed in the art.
The amoun~s of component,~ (A) and (~) that may be prQsent in the emUl~ion compositions of tha present invention may vary widely, and generally compri~e, in total, from about 99.5 to about 91 pQrcent by weigh~ of the total weight of component~ (A) th~ough ~C).
It i~ also contemplated that the emuls70ns of the pre~ent invention can b~ formulated into solid compo~ition~, ~uch a~ antlper~pirant s~icks. The solid fo~ms of the emul3ion~ of the present inventlon ara generally prepar~d by the addition o~ an organlc wax.
Suitabl~ organlc w~xe3 includ~ mineral waxes, such a~ paraffin, etc.; vegetable waxes, such as carnauba, flax, c~ndelLlla, stc.; and animal waxeA ~uch a~ be~s wax.
Chemically th~3a w~xe~ are branched or straigh~ chain hydrocarbons, high molecular weigh~ fatty acid~, high molecular weight alcohol~, or high mole~ular w~ight fatty acld asters. Characteristically waxeQ h~va low viscositie~
~u~t abo~ their melting point. Fo~ u~ herein, ~he waxe~
should hav~ a m~lting point batween about 40 and 65C.

- 15~ 60SI-1423/28 Such a melting point allows for proper application rate~
and prevent~ melting upon storage under ambient condition~.
Preferably the organic wax is a mixture of waxe~ to control the hardnes~q of the stick composition. Thus, a preferred S organic wax i9 a mixture of a w~xy ester for hardnes3, such a~ methyl hydroxyste~rate, and a solid alkanol uch a~
stearyl alcohol. Whera such a mixture of waxes is used, the organic wax might contain 10 to 50 percent by weight solid alkanol and 50 to 90 weight percent waxy e~ter.
Hardnes is also greatly effacted by the proportion of organic wax in the ~tick composition. Preferably, the continuou~ oil matrix contains about 25 to 40 percent by weight organic wax.
The antlperspirant stick is ea~ily prepared by method~ well known in the art. Herein, the methylslloxane fluid, organic wax and emulsi~iar of the present invention are all heated until all componellt~ are liquld and then mixed. Generally the components will llquify betwe~n about 40 and 70~C. Subsequently, the water solution with active lngredient i~ warmed and emulsified into the molten wax a4 i~ known. ~he warm emulsion .i9 poured as closQ to solidificatlon temper~ture a~ possibla into mold~ and allowed to cool. Tha ~olid Ctlck compo~itions containlng the emulsirier3 of the pre~ent invention have improved stability ov~r those de~cribed in the prior art, are drier and do not raquire the addition of o~her ~urfactants although other ~urfactants can be employed if deqired.
The emul~ion~ of the pre~ent invention may ~urther compri~e small amounts o~ non-essential components which are co~monly u~ed in the c08metic art. Examples o~
such components include colorant~; perfumes, visco~ity control additives such a~ solven~s or thickening agents for the continuous phase; and non-volatile organopoly~iloxane~, -16- 60SI-1423~28 such a~ polydimethylsiloxane~ having a vi~cosity of from 10 ~o 10,000 cent~poiso at 25C. In the caq~ of ant~perspirant sticks, talc may be preferably added. The3e additive3 may be added in greater or les~er amount , dependlng on the ne~d~ of the individual u~er.

D l:SCRIP~ION OF l~lE PREFE~RED E~019IMENq~S

The following example~ illu~rate th~ pre~ent invention. They are not to b~ con trued So limit th~ scope of the appended claim~ in any manner whatsoever.

~ o a 3 llter pot is added 235 grams of hydrid~
~iloxane with a~er~g~ structur~ MD20M and 385 gram~ of toluene. The mix~ure is a~eotroped dry.
At 100C, Pt cataly~t (3% platinum cont~nt, chloroplatinic acld, Se~, Unlted States Pa~ent No, 3,220,972) wa~ added (0.4 gram~). To thi~ i5 added 193 grams of decen~-l (1/2 the total amount) controlling tha exotherm at 100-120C.
Following the addl~ion of decen~-l, the mixture is cooled to 1~38 than 70C. To th~ ~ooled mixture i~ then added 10 gram~ of 0.2 ~ sodium aceta e buffer solutlon.
~he mixture is then heated back to 90-100C.
At 100C, 879 gram of a 50/50 mix of toluene ~nd allyl initiated all ethylene oxide polyether, hydroxy capped o~ averag2 550 molecular weight i~ added over a 1 hour poriod.
At the end of th~ allyl poly~ther addltion, another 193 gram~ of decene~ added to complet~ the reac~lon.
The en~ire reac~ion product i~ ~tripped to pot temperature of 130C under nitrogen ~acuum of 10 mm. Tha product i~ then filtered through Celite S45 diatomaceous earth (Johns Manville).

EXAI~PLIS 2 The emulslfier prepared in Example 1 i9 ~mployed in a wat~r-in-oil emulsion. First the oil phase is prepar~
by mixing 17.0 part3 by weight of a heavy mineral o~l, 3.0 partq by weight of SF-1202 (a cyclom~thyl ~iloxan~.fluid, General Electric Comp~ny), and 2.0 part~ by weight of the emul~ifier of Example 1.
Second, the aqueou~ pha~e is prepared by mixing tog~ther 3.0 part-R by weight o~ propylene glycol, 1.0 part by weight o~ sodium chlorid~ and 74.0 part~ by weight of water.
The oily pha~e i~ then added to the aqueous phase with high ~3hear agltation. The emul~ion formed i3 then milled in a Gifford-Wood homogenizer to increa~e stabllity.
The resulting emul~ion pa~ed stab~lity tosting: 60 days at 40C and 4 freezQ/thaw cycle~.

An emulsion i3 prepared in the ~ame pr~cedure a~
in Exampl~ 2, exc~pt tha oily and aqueous phases are vari~d. The oily pha~e comprises: 9.0 part3 by weight of a light mineral oil; 6.0 part by weight of i~opropyl myristate, 3.0 parts by weight of p~rolatum; and 2.5 part~
by weight of the emuls~fi~r of Example 1. The a~ueou3 pha~e comprlses: 5.0 p~rt~ ffl w~ight of glycerine, 1.0 par~
by woight o~ ~odium c~loride and 73.5 part by weigh~ of water.
~ h~ emul~ion forMed i~ found to pa~ ~tability te-~t~ for 60 days at 40C, and 4 fre2z2~thaw cy~les.

-18- 60SI-1423~28 The emul-~ifier prepared in Claim 1 is employed in a watsr-in-oil sunscreen emulsion. The emulsion i5 prepared in th~ samQ manner aY the emul-~ion~ of Claim 2.
The oily phase consist~ of 7.5 part~ by weight of 2-ethylhexyl p-methoxycinnamat~ (a UV8 unscreen~; 5.0 parts by weight of menthyl-o-amlnobenzoate (a W A ~un~creen); 3.~
part~ by w~ight o~ isopropyl myri~tat~ (a~ emoll~ent); 4.0 parts by weight o~ min~ral oil, 55-70 SUS (an emollient);
5.0 p~rtR by weight of SF-1202 (an emollie~t - cyclomethyl siloxane fluid, General ~lectric Company); and 2.0 parts by weight of t:he emul-~ifier o~ Cla$m 1.
q~he aqueou~ pha~e con i3ts of 3.5 partR by welght of glycerine (a humectant); 1.0 part~ by weight of sodium chloride (an eloctrolyte); and 69.0 par~s by welght of water ~a diluent).
The re~ulting emulsion pa~sed 60 days at 40C
stabil~ty tssting. The resulting emul~ion al~o pa~ed stability te3~1ng at 4 fr~eze/tha~w cycles.

EX~MP~E 5 The procedure o~ Example 4 i~ repeated to prepare di~er~nt water-in-oil 3un~creen.
The oily phase con i~ of: 7.5 part~ by weight o~ 2-e~hylhexyl p-mathoxyclnnama~ ( W B ~unscreen~; 5.0 pArt~ by welght of mGnthyl-o-aminobs~zoate ( W A sun~creen)' 3.0 parts by weight o~ i~opropyl myri~tate (emollient~; 4.0 part~ by weight o~ mineral oil, 5S-70 SUS (emollient); 7.0 part4 by welght o SF-1202 (emollient - cyclomethyl siloxan~ fluid, General Elsctric Company~; and 2.5 part~ by w~ight o the emul~ifler of Claim 1.

The aqueouC phase consists of 3.0 part5 by weight o~ glycerine (humectant); 1.5 part~ by weight of 30dium chloride (electrolyte); and 66.5 part by weight of water (a diluent).
The re~ulting emul~ion pas~ed 60 days at 40C
stability testing. The resulting emulsion ~lso pa~sed ~tability te~ting at 4 freeze/thaw cycles. The statis SPF
of the sunscreen wa~ 9.8 when tested on 6 humans by standard SPF determination of sun protection products.

EXAMP~ 6 ~ water-in-oil sun~creen i~ prepared according to the procedure of Exampla 4 with a varied formulation.
Th~ oily phase con~i4ts of: 7.5 parts by weight of 2-ethylhexyl p-methoxycinnamat~ ( W B 3un~creen); 5.0 15 part3 by welght of titanium dioxide ( W A/ W B sunblock); 4.0 parts by weight of isopropyl palmitate (emolllent); 500 part~ by welght of mineral oil, 5l5_70 SUS (emollient); 5.0 parts by weight of SF1202 (emolli~nt - cyclomethyl siloxane fluid, General Electric Company); and 2.0 parts by weight o~ the emul~ifier of Claim 1.
Th~ aqueou~ phase con~i3tY of 3.0 part~ by weight of propylene glycol (humectant); l.0 part~ by weight of ~odium chloride (electroly~e); and 6~.5 part~ by weight of wa~er (a dilu~nt).
~e resulting emulsion pa~ed 60 day~ at 40C
stability testing. ~h~ re ulting emul~ion al~o pa-~ed ~tabllity t~3ting at 4 freeze/~h~w cycl~q.

~XAMPLE~ 7-8 Two wat~r-in-oil sunQcreen~ are prepared according to the procedure of Example 4. The compositlonal data for the two emul~ions are ~et forth below ln Table 1.

~ABLE_1 ExamPle 7 8 Function Oily phas~
2-Ethylhexyl p-metho~y- 7.5 7.5 W B ~un~creen cinnamate 2-Hydroxy-4-methoxy- 3.0 3.0 U V A / U V B
benzophenone ~unsc~n Isopropyl myrl~tate6.0 7.0 Emoll~ent Mineral 011 (55-70 SUS) 6.0 6.0 Emollient SF1202~ 2.0 3.0 Emollient Ganex V-220b - 2.0 Film former Titan~um dioxid~ - 3.0 W A/ W ~
sun3creen Emulsifier~ 2.5 2.5 Emulsifier Aqueous Phaso Propylene glycol 3.0 3.0 Humectant Sodium ~hloride 1.5 1.5 Electrolyte Water 68.5 61.!i Diluent b = Cyclomethyl siloxane fluid, General Electr~ Company = PVP~EICOSENE Copolymer , GAF Corporatlon - Copolymeric ~mul~ifier o~ Exa0pl~ 1 ~ Both ~ormulation~, Example~ 7 and 8, passed 60 day~ at 40C ~tability tasting. The ~ormulation of Example 7 wa~ ~ta~i~ tested ~or SP~ on 3ix humAn~ by s~and~rd 5PF
determina~ion o~ ~un protection pro~uct~. The re~ulting SPF obtalned wa~ 15.3.

~21- 60SI-1423/28 EXA~PLE 9 The procedure of Exampl~ 4 wa~ followed, Yarying the formulation, to prepare a sun~creen wa~er-in-oil emul~ion.
The oily pha~e consistad of: 7.5 parts by weight of 2-ethylhexyl p-me~hoxycinnAmate ( W B ~unscreen); 4.0 part~ by weight of 2-ethylhexyl salicylatQ ( W B ~unscreen);
2.0 part~ by walght of 2-hydroxy-4-methoxyb2nzophenon2 ( W A/ W B ~un~creen3; 8.0 part~ by weight of myri~tyl propionata (emollient); 7.0 part~ by weight of SF1202 (emollient - cyclomethyl siloxan~ ~luid, G~neral Electric Company); and 2.5 part~ by welght of the emulsifier of Example 1.
The a~uoou~ pha~e con3i~ted of 3.0 part~ by weight of propylene glycol (humectant); 1.5 parts by wQight of ~odium chloride ~Qlectrolyte); and 6~.5 p~rts by w~ight o~ water (diluent).
The ~un~creen emul~lon pas~ed 60 days at 40C
stabillty testlng, and pa~sed ~tabillty te~ting at 4 fre~ze/thaw cyclss.
Ths abo~e mentioned pat~ant~ and publications are lncorporated hereln by r~fer~nc~.
Many ~ariations o~ the pre~ent invent~on wlll ~ugge~t themselve~ to t~o~e skilled in this ar~ in llght of th~ above detalled descrlption. All such obviou~
modlfi~a~on3 are wi~hin ths full $ntended ~cop~ o~ the appended clalms.

Claims (30)

1. A silicone polyether alkyl copolymer water-in-oil emulsifier of the general formula:
MD'xD"yM
wherein represents trimethylsiloxy endcapping units;
D' represents alkyl siloxy units of the general formula (CH3)R'SiO2/2 where R' is an alkyl group having from 6 to 30 carbon atoms;
D" is an oxyalkylene siloxy unit of the general formula (CH3)R2SiO2/2 where R2 is a polyoxyalkylene ether residue of the formula -(R4)p - (OR3)n-OR5 wherein each individual R3 is an alkylene radical having from 2 to 6 carbon atoms, R4 is an alkylene radical having from 2 to 20 carbon atoms, R5 is hydrogen or a hydrocarbon radical of from 1 to about 12 carbon atoms, n has a value of from about 5 to about 20, and p has a value of zero or 1, x is from 1 to about 29, and y is from 1 to about 29;
with the proviso that x + y is from about 2 to about 30.

2. A copolymer as defined in Claim 1, wherein R`
is an alkyl group of from about 8 to about 18 carbon atoms.

3. A copolymer as defined in Claim 2, wherein R' is and alkyl group of 10 carbon atom and D' represents methyl decylsiloxy units.

4. A copolymer as defined in Claim 1, wherein D"
represents methyl polyethoxy siloxy units.

5. A copolymer as defined in Claim 1, wherein D"
has an average R molecular weight of from about 300 to about 800.

6. A copolymer as defined in Claim 1, wherein x is from 1 to about 20, y is from 1 to about 20 and x+y is from about 15 to about 25.

7. A copolymer as defined in Claim 6, wherein x is about 16, y is about 4 and x+y is about 20.

8. A copolymer a defined in Claim 1, wherein D' represents methyl decyliloxy units, D" represents methyl polyethoxy siloxy units and x+y is about 20.

9. A process for preparing a silicon polyether/alkyl copolymer comprising the steps of:
(a) reacting a silicone hydride fluid of the formula:
MDqM (I) wherein M represents trimethylsiloxy units, D represents methylhydrosiloxly units and q is from about 2 to about 30, with a first portion of an alpha olefin of from about 6 to about 30 carbon atoms to form a compound of the formula:
MDq-fD'fM (II) wherein M, D and q are as above defined; and D' represents and alkylmethylsiloxy unit of the formula CH3RSiO wherein R
represents an alkyl radical of from about 6 to about 30 carbon atoms, and f is from about 1 to about 29;
(b) reacting the compound of formula (II) with an allyl polyether of from 2 to about 12 carbon atoms to form a compound of the formula:
MDq-f-yD'fD"yM (III) wherein M, D, D', q and f are are above defined and D"
represents an oxyalkylene siloxy unit of the general formula (CH3)R2SiO2/2 where R2 is a polyoxyalkylene ether residue of the formula -(R4)p - (OR3)n-OR5 wherein each individual R3 is an alkylene radical having from 2 to 6 carbon atoms, R4 is an alkylene radical having from 2 to 20 carbon atoms, R5 is hydrogen or a hydrocarbon radical of from 1 to about 12 carbon atoms, n has a value of from about 5 to about 20, and p has a value of zero or 1, and y is from about 1 to about 29; and -24- 60SI-l423/28 (c) reacting the compound of formula (III) with a second portion of said alpha olefin to form a compound of the formula MD'xD"yM (IV) wherein M, D', D" and y are as defined above, and x is from 1 to about 29 and is equal to q-y; and wherein said steps (a), (b) and (c) are carried out in the presence of a small effective amount of a catalyst for effecting said reactions.

10. A process as defined in Claim 9, wherein said alpha olefin has from about 8 to about 15 carbon atoms and R' represents an alkyl radical of from about 8 to about 15 carbon atoms.

11. A process as defined in Claim 10, wherein said alpha olefin is decene-l, R' represents an alkyl radical of 10 carbon atoms and D' represents methyl decylsiloxy units.

12. A process as defined in Claim 9, wherein D"
represents methyl polyethoxy siloxy units.

13. A process as defined in Claim 12, wherein D10 has an average R2 molecular weight of from about 300 to about 800.

14. A process as defined in Claim 9, wherein q is an integer of from about 15-25, x is an integer of from about 1 to about 20, and y is an integer of from about l to about 20.

15. A process as defined in Claim 9 wherein q is 20, x is 16 and y is 4.

16. A process as defined in Claim 15 wherein the first portion of olefin is about equal in amount to the second olefin portion.

17. A process as defined in Claim 9, wherein said catalyst is a platinum containing catalyst.

18. A process as defined in Claim 9, wherein said catalyst is present in an amount ranging from about 0.05 to about 0.5 weight percent based on the weight of the starting silicone hydride.

19. A water-in-oil emulsion comprising:
(A) from about 10 to about 50 parts by weight of an oily phase;
(B) from about 40 to about 80 parts by weight of a discontinuous phase; and (C) from about 1 to about 15 parts by weight the silicon polyether alkyl copolymer emulsifiers as defined in Claim 1.

20. A water-in-oil emulsion as defined in Claim 19 wherein said oily phase (A) comprises an oil selected from the group consisting of mineral oils, petrolatum, paraffinic hydrocarbon liquids and mixtures of any of the foregoing.

21. A water-in-oil emulsion as defined in Claim 19, wherein said oily phase comprises a volatile liquid having a normal boiling point of less than 250°C, said volatile liquid being selected from the group consisting of methylsiloxane fluids having the average unit formula (CH3)aSiO(4-a)/2 wherein a has an average value of from 2 to 3 inclusive.

22. A water-in-oil emulsion as defined in Claim 21 wherein said volatile methylsiloxane fluid consisting essentially of dimethylsiloxane units.

23. A water-in-oil emulsion as defined in Claim 22 wherein said methylsiloxane fluids are cyclic siloxanes of the general formula ((CH2)SiO)b wherein b is an integer of from 3 to 6.

24. A water-in-oil emulsion as defined in Claim 19, wherein aid aqueous phase (B) comprises water.

25. A water-in-oil emulsion as defined in Claim 19 further comprising (D) an effective amount of an efficacious additive.

26. A water-in-oil emulsion as defined in Claim 25, wherein said additive is selected from the group consisting of an antiperspirant, a humectant, an insect repellent, an odorant, a deodorant, an emollient, an antiseptic, a sunscreen, a cleansing agent, a suitable pharmaceutical, a pigment, a biocide and mixtures of any of the foregoing.

27. A water-in-oil emulsion as defined in Claim 26 wherein said additive comprises a sunscreen.

28. A water-in-oil emulsion as defined in Claim 26 wherein said additive comprises an antiperspirant selected from water soluble astringents.

29. A water-in-oil emulsion as defined in Claim 28 in the form of stick further comprising an organic wax.

30. The invention as defined in any of the preceding claims including any further features of novelty disclosed.